US5523280A - Phenylpyrazole fungicides - Google Patents

Phenylpyrazole fungicides Download PDF

Info

Publication number
US5523280A
US5523280A US07/959,131 US95913192A US5523280A US 5523280 A US5523280 A US 5523280A US 95913192 A US95913192 A US 95913192A US 5523280 A US5523280 A US 5523280A
Authority
US
United States
Prior art keywords
group
alkyl
alkoxy
carbonyl
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US07/959,131
Other languages
English (en)
Inventor
Alain Chene
Raymond Peignier
Jean-Pierre A. Vors
Jacques Mortier
Richard Cantegril
Denis Croisat
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience SA
Original Assignee
Rhone Poulenc Agrochimie SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Agrochimie SA filed Critical Rhone Poulenc Agrochimie SA
Assigned to RHONE-POULENC AGROCHIMIE reassignment RHONE-POULENC AGROCHIMIE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CHENE, ALAIN, PEIGNIER, RAYMOND, CANTEGRIL, RICHARD, CROISAT, DENIS, MORTIER, JACQUES, VORS, JEAN-PIERRE A.
Priority to US08/470,591 priority Critical patent/US5663119A/en
Application granted granted Critical
Publication of US5523280A publication Critical patent/US5523280A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to new derivatives of the 3-phenylpyrazole family, to processes for their preparation, to the compositions which contain them and to their use for the protection of plants against fungal diseases.
  • the subject of the invention is 3-phenylpyrazole derivatives, characterised in that they are of formulae: ##STR2## in which:
  • X is:
  • alkyl, alkenyl, alkynyl, alkoxy or alkylthio group each of these groups being halogenated or nonhalogenated
  • a phenyl or phenoxy group each of these groups being optionally substituted by C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 1 -C 3 alkoxy,
  • alkylsulphinyl or alkylsulphonyl group it being understood that the alkyl part of all the above groups comprises 1 to 4 carbon atoms unless otherwise defined, and the alkenyl and alkynyl groups contain 2 to 4 carbon atoms;
  • Y and Z which are identical or different, are:
  • phenyl, phenyloxy or phenylthio or benzyl substituted or unsubstituted on the nucleus by C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 1 -C 3 alkoxy,
  • Y and Z can also be joined together via a carbon bridge comprising 1 to 4 atoms, at least one of which can be replaced by an oxygen, sulphur or nitrogen atom, it being possible for the carbons of this bridge to additionally be substituted or unsubstituted by at least one halogen atom and/or at least one alkyl, alkoxy or alkylthio group as defined above, and it being possible for each to be also joined, via a double bond, to an oxygen atom;
  • R is:
  • n is an integer equal to zero or two
  • R 1 is:
  • a phenyl or 3-pyridyl it being possible for each to be substituted by at least one halogen atom or one nitro, alkyl, haloalkyl, alkoxy or haloalkoxy group, the alkyl part of these four groups comprising 1 to 4 carbon atoms;
  • alkyl or alkoxy group each comprising 1 to 6 carbon atoms and being substituted or unsubstituted by one or more halogen atoms or alkoxy groups containing 1 to 3 carbon atoms;
  • alkenyl or alkynyl or alkenoxy group each comprising 3 to 6 carbon atoms
  • a phenyl group substituted or unsubstituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro group or an alkyl, haloalkyl, alkoxy or haloalkoxy comprising 1 to 4 carbon atoms;
  • R 2 is:
  • alkyl containing 1 to 6 carbon atoms optionally substituted by a substituent chosen from the group comprising cyano, alkoxy, cycloalkyl containing 3 to 7 carbon atoms, alkylcarbonyl, alkoxycarbonyl, mono- or dialkylaminocarbonyl, alkylsulphinyl, alkylsulphonyl or dialkylamino, the alkyl part of these groups comprising 1 to 6 carbon atoms;
  • phenyl or benzyl optionally substituted by a substituent chosen from the group comprising a halogen atom or a cyano, alkyl, alkoxy, haloalkyl or haloalkoxy containing 1 to 9 halogen atoms, alkylcarbonyl or alkoxycarbonyl group, the alkyl part of these groups comprising 1 to 6 carbon atoms;
  • R 3 is a group:
  • a substituent chosen from the group comprising a halogen atom or a cyano, alkyl, alkoxy, haloalkyl or haloalkoxy containing 1 to 9 halogen atoms, alkylcarbonyl or alkoxycarbonyl group, the alkyl part of these groups comprising 1 to 6 carbon atoms;
  • dialkylaminoalkyl the alkyl part of these groups comprising 1 to 6 carbon atoms; cycloalkyl or cycloalkylalkyl (alkyl containing 1 to 4 carbon atoms) containing 3 to 7 carbon atoms; or phenethyl, optionally substituted by a substituent chosen from the group comprising a halogen atom, a cyano group, or an alkyl or alkoxy group each containing 1 to 4 carbon atoms;
  • R 2 and R 3 can additionally form, with the
  • nitrogen atom to which they are joined a nitrogen-containing ring containing 6 atoms, 4 of which are carbon atoms, optionally substituted, and the fifth is a carbon atom or a heteroatom such as oxygen, sulphur or nitrogen which can be substituted by an alkyl group containing 1 to 6 carbon atoms, it being possible for the nitrogen-containing ring itself to be substituted by one or two substituents chosen from the group comprising cyano, alkylcarbonyl, alkoxycarbonyl, mono- or dialkylaminocarbonyl, alkylsulphinyl or alkylsulphonyl, the alkyl part of these groups comprising 1 to 6 carbon atoms, or phenylsulphinyl or phenylsulphonyl;
  • n 1 or 2
  • R 4 is a cyano, nitro, alkylcarbonyl, phenylcarbonyl, alkoxycarbonyl, mono- or dialkylaminocarbonyl, P(O) (alkoxy) 2 , P(O) (benzyloxy) 2 , P(O) (phenoxy) 2 , trialkylsilyl or phenyl group, it being understood that the alkyl radical of these groups comprises 1 to 4 carbon atoms and is optionally halogenated and that the phenyl nucleus of the aromatic radicals can be substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro group or an alkyl, alkoxy, haloalkyl, haloalkoxy or alkoxycarbonyl radical, the alkyl part of each of these radicals comprising 1 to 4 carbon atoms;
  • R 5 is a hydrogen atom or an alkyl containing 1 to 4 carbon atoms
  • X is an oxygen atom or a group S(O) n , in which:
  • n is an integer equal to zero or two
  • R 6 is:
  • alkyl containing 1 to 4 carbon atoms optionally substituted by a substituent chosen from the group comprising a halogen atom or a cyano, alkoxy, phenoxy, benzyloxy or trialkylsilyl group, the alkyl part of each of these radicals comprising 1 to 4 carbon atoms and the phenyl nuclei being able to be substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro group or an alkyl, alkoxy, haloalkyl or haloalkoxy radical, the alkyl part of each of these radicals comprising 1 to 4 carbon atoms;
  • phenyl or benzyl which can be substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro group or an alkyl, alkoxy, haloalkyl or haloalkoxy radical (1 to 4 carbon atoms);
  • R 7 is a hydrogen atom or a haloalkyl or alkoxy group, each containing 1 to 4 carbon atoms,
  • R 8 is a halogen atom or a hydroxyl, alkoxy or O--C(O)R 9 group with
  • R 9 being a hydrogen atom, an alkyl, haloalkyl or alkenyl containing 1 to 4 carbon atoms, tetrahydrofuryl, tetrahydropyranyl or alkoxycarbonyl group, the alkyl part of each of these radicals comprising 1 to 6 carbon atoms;
  • X is an oxygen or sulphur atom
  • R 10 is:
  • alkyl group containing 1 to 6 carbon atoms optionally substituted by a substituent chosen from the group comprising a halogen atom or a cyano, nitro, alkylcarbonyl, alkoxycarbonyl or mono- or dialkylaminocarbonyl group, the alkyl pan of each of these radicals comprising 1 to 4 carbon atoms, or a cycloalkyl group containing 3 to 6 carbon atoms;
  • an alkenyl or alkynyl group containing 3 to 6 carbon atoms, optionally substituted by a phenyl which can be Substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro group or an alkyl, alkoxy, haloalkyl or haloalkoxy radical, the alkyl part of each of these radicals comprising 1 to 4 carbon atoms;
  • a phenyl, benzyl, 2-pyridyl, 3-pyridyl or 4-pyridyl group it being possible for the nuclei to be substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro or cyano group, or an alkyl, alkoxy, haloalkyl, haloalkoxy, alkylcarbonyl or alkoxycarbonyl radical, the alkyl part of each of these radicals comprising 1 to 4 carbon atoms;
  • R 11 is a hydrogen atom or an alkyl containing 1 to 4 carbon atoms
  • X is an oxygen atom or the group S(O) p , with p equal to zero or 2;
  • R 12 is an alkyl containing 1 to 4 carbon atoms, optionally substituted by a halogen atom or an alkoxy containing 1 to 4 carbon atoms; an alkenyl or alkynyl group, containing 3 to 6 carbon atoms; a phenyl or benzyl group which can be substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro group or an alkyl, alkoxy, haloalkyl or haloalkoxy radcial (1 to 4 carbon atoms);
  • R 13 and R 14 which are identical or different, are each:
  • alkyl containing 1 to 4 carbon atoms optionally substituted by a cyano, alkylcarbonyl, alkoxycarbonyl or dialkylaminocarbonyl group, halogen atom or an alkoxy containing 1 to 4 carbon atoms;
  • a phenyl or benzyl group which can be substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro or cyano group or an alkyl, alkoxy, haloalkyl, haloalkoxy or alkoxycarbonyl radical, the alkyl part of each of these radicals comprising 1 to 4 carbon atoms;
  • R 11 is as defined above and
  • R 15 is a heterocyclic group NC 4 R 16 R 17 T, in which R 16 and R 17 , which are identical or different, are a hydrogen atom or an alkyl or alkoxycarbonyl group, each containing 1 to 3 carbon atoms, and T is an oxygen or sulphur atom, or a carbonyl or N--R 18 group, in which R 18 is a hydrogen atom or an alkyl, formyl, alkylcarbonyl or alkoxycarbonyl group, the alkyl part of each of these radicals comprising 1 to 4 carbon atoms;
  • X is an oxygen or sulphur atom
  • R 19 is:
  • an alkyl group containing 1 to 6 carbon atoms optionally substituted by a substituent chosen from the group comprising a halogen atom or a cyano group; a cycloalkyl group containing 3 to 6 carbon atoms, optionally substituted by an alkyl containing 1 to 3 carbon atoms; trialkylsilyl, phenylsulphonyl, optionally substituted by at least one halogen atom or an alkyl group; alkoxycarbonyl or dialkylaminocarbonyl; the alkyl part of each of the above radicals comprising 1 to 4 carbon atoms;
  • alkenyl or alkynyl group containing 2 to 6 carbon atoms optionally substituted by a phenyl which can be substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro group or an alkyl radical;
  • a phenyl, benzyl, 2-pyridyl, 3-pyridyl or 4-pyridyl group it being possible for the nuclei to be substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro or cyano group, or an alkyl, alkoxy, haloalkyl, haloalkoxy, alkylcarbonyl or alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl radical, the alkyl part of each of these radicals comprising 1 to 4 carbon atoms;
  • a phenylalkyl group or a heterocyclylalkyl group in which the alkyl part comprises 1 to 4 carbon atoms and the heterocyclyl part can be 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-furyl, 3- furyl, 2-thienyl or 3-thienyl, it being possible for the nuclei to be substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro group, or an alkyl, alkoxy, haloalkyl, haloalkoxy, alkylcarbonyl or alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl radical;
  • X is an oxygen or sulphur atom
  • R 20 and R 21 are each:
  • a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms optionally substituted by a substituent chosen from the group comprising a halogen atom or a cyano, alkylcarbonyl, alkoxycarbonyl or dialkylaminocarbonyl group, the alkyl part of each of the above radicals comprising 1 to 4 carbon atoms;
  • a phenyl or benzyl group it being possible for the nuclei of each to be substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, a nitro or cyano group, or an alkyl, alkoxy, haloalkyl, haloalkoxy, alkylcarbonyl or alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl radical, the alkyl part of each of these radicals comprising 1 to 4 carbon atoms;
  • R 20 and R 21 can additionally form, with the nitrogen atom to which they are Joined, a ring containing 6 atoms, 4 of which are optionally substituted carbon atoms and the fifth of which is a carbon atom or a heteroatom such as oxygen, sulphur or nitrogen;
  • R 22 , R 23 and R 24 which are identical or different, are each an alkyl group containing 1 to 4 carbon atoms, or a phenyl or benzyl group,
  • X is an oxygen or sulphur atom
  • R 25 and R 26 which are identical or different, are each an alkyl or alkoxy group containing 1 to 4 carbon atoms, or a phenyl, phenoxy, benzyl or benzoxy group.
  • X is preferably a chlorine or bromine atom.
  • R is an alkyl(1 to 3 carbon atoms)carbonyl, alkoxy(1 to 3 carbon atoms)carbonyl, phenylcarbonyl or phenoxycarbonyl.
  • the derivatives according to the invention can be prepared by various processes known per se, especially in the compilations "Comprehensive Heterocyclic Chemistry", A. R. Katritzky and C. W. Rees, 1984, Vol. 5, pages 239 to 241 and 263, Pergamon Press; "Advances in Heterocyclic Chemistry", A. N. Kost and I. I. Grandberg, 1966, Vol. 6, pages 391 to 396, Academic Press and "The Chemistry of Heterocyclic Compounds", L. C. Behr, R. Fusco and C. H. Jardoe, 1967, J. Wiley & Sons.
  • a first process consists in reacting a 3-phenylpyrazole of formula II, in which Y and Z have the same meaning as in the formula I, with a halogenating agent.
  • chlorinating agent chlorine, preferably in aqueous medium, such as in water, or in an organic medium such as acetic acid or carbon tetrachloride, or else hypochlorous acid, hydrochloric acid in the presence of hydrogen peroxide in acetic acid, or else sulphuryl chloride or an N-chloroimide, such as N-chlorosuccinimide, in a chlorinated solvent such as dichloromethane, or else phosphorus pentachloride.
  • chlorinating agent chlorine, preferably in aqueous medium, such as in water, or in an organic medium such as acetic acid or carbon tetrachloride, or else hypochlorous acid, hydrochloric acid in the presence of hydrogen peroxide in acetic acid, or else sulphuryl chloride or an N-chloroimide, such as N-chlorosuccinimide, in a chlorinated solvent such as dichloromethane, or else phosphorus pentachloride.
  • Chlorination can be carried out with chlorine in organic solvent medium, preferably a lower carboxylic acid, at a temperature from 16° to 30° C., preferably at room temperature, the reactants being in a substantially stoichiometric molar ratio.
  • Chlorination can also be carried out with N-chlorosuccinimide in organic solvent medium, preferably a chlorinated solvent such as dichloromethane or 1,2-dichloroethane, at a temperature of 0° C. to 80° C. and preferably from 20° C. to 50° C., the reactants being in a substantially stoichiometric molar ratio.
  • brominating agent bromine, preferably in an aqueous solvent such as water, in acidic medium, for example nitric or acetic acid, in the presence or absence of a base such as sodium acetate, or in an organic solvent, such as, for example, chloroform, or else pyridinium perbromide.
  • aqueous solvent such as water
  • acidic medium for example nitric or acetic acid
  • a base such as sodium acetate
  • organic solvent such as, for example, chloroform, or else pyridinium perbromide.
  • Bromination can be carried out, for example, with bromine in organic solvent medium such as a lower carboxylic acid, at a temperature of 16° C. and preferably at room temperature.
  • organic solvent medium such as a lower carboxylic acid
  • iodinating agent iodine in the presence of hypoiodous acid or in the presence of a base such as an alkali metal hydroxide or a basic salt such as sodium acetate, or in the presence of a nickel(II) salt. It is also possible to use iodine with the silver(I) salt of the pyrazole of formula I. It is also possible to use N-iodosuccinimide, as indicated above for N-chlorosuccinimide.
  • Fluorination can be carried out from derivatives of formula V, in which Y and Z have the same meaning as in the formula I, by preparation of the diazonium tetrafluoroborate derivative derived from the 4-amino group and then by irradiation of this compound.
  • a second process known per se for the preparation of the derivatives of formula I according to the invention consists in reacting a 4-formyl-3-phenylpyrazole of formula IV with bromine in acetic acid to give 4-bromo-3-phenylpyrazole.
  • the compounds of formula II can be prepared, in a way known per se, by reaction with hydrazine of a derivative of formula III, in which X is a hydrogen atom and W is a hydroxyl radical or a chlorine atom and Y and Z have the same meanings as in the formula I.
  • the derivatives of formula III in which X is a hydrogen atom and W a dialkylamino group, Y and Z being defined as above, can be obtained, in a way known per se, by reaction of acetophenones of formula VI, in which Y and Z are defined as above, with amide acetals, ester aminals or orthoaminals, preferably in the absence of organic solvent with dialkyl (preferably dimethyl or diethyl) acetals of N,N-dimethylformamide, at a temperature of 20° C. to 130° C. and preferably from 70° C. to 130° C.
  • the pH of the reaction mixture is then brought to 6 by addition of a 1N aqueous hydrochloric acid solution.
  • a 1N aqueous hydrochloric acid solution After extracting with ether, drying over MgSO 4 , evaporation and purification by passing through a silica column (heptane/ethyl acetate 9/1), 5 g of a pale yellow powder, 1-(2,2-difluoro-1,3-benzodioxol-4-yl)-1,3-butanedione, are obtained.
  • reaction mixture Treatment of the reaction mixture is carried out by addition of ethyl acetate, washing with water and with a saturated sodium chloride solution. After drying over MgSO 4 , evaporation of the organic phase leads to the following being obtained: 5-amino-3-(2,2-difluoro-1,3-benzodioxol-4-yl)-4-thiocyanatopyrazole.
  • An aqueous suspension of the active material to be tested is prepared, by fine milling, having the following composition:
  • Tween 80 (oleate of polyoxyethylenated derivative of sorbitan) diluted to 10% in water: 0.3 ml
  • This aqueous suspension is then diluted with water to obtain the desired concentration of active material.
  • Tomatoes cultivated under glass (variety Marmaude), 30 days old, are treated by spraying with aqueous suspensions as defined above and at various concentrations of the test compound.
  • the leaves are-cut and put in a Petri dish (diameter 14 cm), the bottom of which was covered beforehand with a wet filter paper disc (10 leaflets per dish).
  • the inoculum is then introduced, using a syringe, by deposition of drops (3 per leaflet) of a suspension of spores of Botrytis cinerea, which are sensitive to benzimidazoles or resistant to benzimidazoles, obtained from 15-day cultures and then suspended at a concentration of 150,000 units per cm 3 .
  • Inspection is carried out 6 days after infection by comparison with an untreated control.
  • Botrytis sensitive to benzimidazoles 9, 13, 17, 19, 21, 22, 23, 24, 25, 71, 73, 74, 88, 95, 99, 100, 104, 105, 107, 108, 113, 114, 116, 120, 122, 123, 124, 128, 133, 135, 147, 166, 172, 173, 175, 176, 177, 179, 180, 181, 182, 183, 184, 185.
  • An aqueous suspension of the active material to be tested is prepared, by fine milling, having the following composition:
  • Tween 80 (oleate of polyoxyethylenated derivative of sorbitan) diluted to 10% in water: 0.3 ml
  • This aqueous suspension is then diluted with water to obtain the desired concentration of active material.
  • Rice seeded in small pots in a 50/50 mixture of enriched peat and pozzolana, is treated at the 10 cm high stage by spraying with the above aqueous suspension.
  • the rice plants are incubated for 24 hours (25° C., 100% relative humidity) and are then put in an observation cell, under the same conditions, for 7 days.
  • Reading is carried out 6 days after infection.
  • An aqueous suspension of the active material to be tested is prepared, by fine milling, having the following composition:
  • This aqueous suspension is then diluted with water to obtain the desired concentration of active material.
  • Vine cuttings (Vitis vinifera, variety Chardonnay) are cultivated in small pots. When these plants are 2 months old (8 to 10 leaf stage, 10 to 15 cm in height), they are treated by spraying with the above aqueous suspension.
  • each plant After drying for 24 hours, each plant is infected by spraying with an aqueous suspension of spores of Plasmopara viticola, obtained from a 17-day culture and then suspended at a concentration of 100,000 units per cm 3 .
  • the infected plants are then incubated for two days at approximately 18° C., in an atmosphere saturated with moisture, and then for 5 days at approximately 20°-22° C. at 90-100% relative humidity.
  • compositions which can be used as herbicidal agents, contain a compound according to the invention, as described earlier, as active material mixed with solid or liquid vehicles, which are acceptable in agriculture, and surface-active agents which are also acceptable in agriculture.
  • the inert and conventional vehicles and the conventional surface-active agents can be used.
  • compositions according to the invention usually contain from approximately 0.05 to 95% (by weight) of a compound according to the invention, one or more solid or liquid vehicles and, optionally, one or more surface-active agents.
  • vehicle denotes a natural or synthetic, organic or inorganic material with which the compound is combined to facilitate its application to the plant, to seeds or to the ground.
  • This vehicle is thus generally inert and it must be acceptable in agriculture, especially on the treated plant.
  • the vehicle can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers and the like) or liquid (water, alcohols, especially butanol, and the like).
  • the surface-active agent can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surface-active agents.
  • ionic or nonionic type a mixture of such surface-active agents.
  • the presence of at least one surface-active agent is generally indispensable when the compound
  • compositions according to the invention are themselves in fairly diverse, solid or liquid forms.
  • the compounds of formula (I) can also be used in the form of powders for dusting; it is also possible to use a composition comprising 50 g of active material and 950 g of talc; it is also possible to use a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and milled and the mixture is applied by dusting.
  • the emulsifiable or soluble concentrates most often comprise 10 to 80% of active material while emulsions or solutions ready for application contain 0.001 to 20% of active material.
  • the emulsifiable concentrates can contain, when this is necessary, 2 to 20% of suitable additives such as stabilising agents, surface-active agents, penetrating agents, corrosion inhibitors, dyes or the abovementioned adhesives.
  • the suspension concentrates are prepared so as to obtain a stable fluid product which does not settle out and they generally contain from 10 to 75% of active material, from 0.5 to 15% of surface-active agents, from 0.1 to 10% of thixotropic agents and from 0 to 10% of suitable additives, such as antifoaming agents, corrosion inhibitors, stabilising agents, penetrating agents and adhesives and, as vehicle, water or an organic liquid in which the active material is insoluble or nearly insoluble: certain organic solid materials or inorganic salts can be dissolved in the vehicle to aid in preventing sedimentation or as antigels for water.
  • a suspension concentrate composition is given here as an example:
  • Wettable powders are generally prepared so that they contain 20 to 95% of active material, and they generally contain, in addition to the solid vehicle, from 0 to 30% of a wetting agent, from 3 to 20% of a dispersing agent and, when this is necessary, from 0.1 to 10% of one or more stabilising agents and/or other additives, such as penetrating agents, adhesives, or anticlumping agents, dyes, and the like.
  • the active materials are intimately mixed, in suitable mixers, with the additional substances and the mixture is milled with mills or other suitable grinders. Powders to be sprayed are thereby obtained with advantageous wettability and suspensibility; they can be suspended in water at any desired concentration and these suspensions can be used very advantageously in particular for application to plant leaves.
  • Pastes can be produced in place of wettable powders.
  • the conditions and modes of production and use of these pastes are similar to those of wettable powders or powders to be sprayed.
  • This wettable powder contains the same ingredients as in the above example, in the proportions below:
  • Aqueous dispersions and emulsions for example the compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, are within the general scope of the present invention.
  • Emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency, like that of a "mayonnaise".
  • the compounds according to the invention can be formulated in the form of water-dispersable granules, also within the scope of the invention.
  • These dispersible granules with a bulk density generally of between approximately 0.3 and 0.6, have a particle size generally of between approximately 150 and 2000 and preferably between 300 and 1500 microns.
  • the active material content of these granules is generally between approximately 1% and 90%, and preferably between 25% and 90%.
  • the rest of the granule is essentially composed of a solid vehicle and, optionally, of surface-active adjuvants which confer water-dispersibility properties on the granule.
  • These granules can be essentially of two distinct types according to whether the vehicle held is soluble or insoluble in water.
  • the vehicle When the vehicle is water-soluble, it can be inorganic or, preferably, organic. Excellent results were obtained with urea.
  • the latter is preferably inorganic, such as, for example, kaolin or bentonire.
  • surface-active agents in a proportion of 2 to 20% by weight of the granule of which more than half consists of, for example, at least one dispersing agent, essentially anionic, such as an alkali metal or alkaline-earch metal polynaphthalenesulphonate or an alkali metal or alkaline-earth metal lignosulphonate, the remainder consisting of nonionic or anionic wetting agents such as an alkali metal or alkaline-earth metal alkylnaphthalenesulphonate.
  • dispersing agent essentially anionic, such as an alkali metal or alkaline-earch metal polynaphthalenesulphonate or an alkali metal or alkaline-earth metal lignosulphonate, the remainder consisting of nonionic or anionic wetting agents such as an alkali metal or alkaline-earth metal alkylnaphthalenesulphonate.
  • the granules according to the invention can be prepared by mixing the necessary ingredients and then granulating according to several techniques known per se (granulator, fluid bed, sprayer, extrusion, and the like). The preparation generally finishes with a grinding followed by a sieving to the particle size chosen within the limits mentioned above.
  • active material compound No. 1
  • urea in the form of pearls 90% by weight of active material (compound No. 1) and 10% of urea in the form of pearls are mixed in a mixer. The mixture is then milled in a pin mill. A powder is obtained which is moistened with approximately 8% by weight of water. The moist powder is extruded in a perforated-roller extruder. A granular material is obtained which is dried, and then crushed and sieved, so as to respectively keep only the granules with a size of between 150 and 2000 microns.
  • This mixture is granulated on a fluid bed in the presence of water and then dried, crushed and sieved so as to obtain granules with a size of between 0.15 and 0.80 mm.
  • granules can be used alone or in solution or dispersion in water so as to obtain the required dose. They can also be used to prepare combinations with other active materials, especially fungicides, the latter being in the form of wettable powders or granules or aqueous suspensions.
  • compositions which are suitable for storage and transportation they most advantageously contain from 0.5 to 95% (by weight) of active substance.
  • Another subject of the invention is the use of the compounds according to the invention for combating fungal diseases in plants by preventative or curative treatment of the latter or of their growth site.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US07/959,131 1991-10-09 1992-10-09 Phenylpyrazole fungicides Expired - Fee Related US5523280A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US08/470,591 US5663119A (en) 1991-10-09 1995-06-07 Phenylpyrazole fungicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9112647A FR2682379B1 (fr) 1991-10-09 1991-10-09 Nouveaux phenylpyrazoles fongicides.
FR9112647 1991-10-09

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US08/470,591 Division US5663119A (en) 1991-10-09 1995-06-07 Phenylpyrazole fungicides

Publications (1)

Publication Number Publication Date
US5523280A true US5523280A (en) 1996-06-04

Family

ID=9417894

Family Applications (2)

Application Number Title Priority Date Filing Date
US07/959,131 Expired - Fee Related US5523280A (en) 1991-10-09 1992-10-09 Phenylpyrazole fungicides
US08/470,591 Expired - Fee Related US5663119A (en) 1991-10-09 1995-06-07 Phenylpyrazole fungicides

Family Applications After (1)

Application Number Title Priority Date Filing Date
US08/470,591 Expired - Fee Related US5663119A (en) 1991-10-09 1995-06-07 Phenylpyrazole fungicides

Country Status (31)

Country Link
US (2) US5523280A (cs)
EP (1) EP0538156A1 (cs)
JP (1) JP3504679B2 (cs)
KR (1) KR100255682B1 (cs)
CN (2) CN1050834C (cs)
AP (1) AP377A (cs)
AU (1) AU665782B2 (cs)
BG (1) BG62255B1 (cs)
BR (1) BR9204011A (cs)
CA (1) CA2080195A1 (cs)
CZ (1) CZ283473B6 (cs)
EC (1) ECSP920870A (cs)
EG (1) EG19893A (cs)
FI (1) FI111541B (cs)
FR (1) FR2682379B1 (cs)
HR (1) HRP921023A2 (cs)
HU (1) HU215380B (cs)
IL (1) IL103408A (cs)
MA (1) MA22675A1 (cs)
MX (1) MX9205768A (cs)
MY (1) MY113369A (cs)
NZ (1) NZ244671A (cs)
PH (1) PH30759A (cs)
PL (2) PL299872A1 (cs)
RO (1) RO110944B1 (cs)
RU (1) RU2072991C1 (cs)
SI (1) SI9200254A (cs)
SK (1) SK279059B6 (cs)
YU (1) YU48425B (cs)
ZA (1) ZA927718B (cs)
ZW (1) ZW16192A1 (cs)

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5817682A (en) * 1992-07-16 1998-10-06 Basf Aktiengesellschaft Heteroaromatic compounds and crop protection agents containing them
US5856514A (en) * 1993-06-03 1999-01-05 Rhone-Poulenc Agrochimie Arylpyrazole fungicides
US5945382A (en) * 1992-04-27 1999-08-31 Rhone-Poulenc Agrochimie Fungicidal arylpyrazoles
WO2000013508A1 (en) * 1998-09-09 2000-03-16 Ishihara Sangyo Kaisha, Ltd. Fused-benzene derivatives useful as herbicides
US6054413A (en) * 1996-09-19 2000-04-25 Basf Aktiengesellschaft 1-sulfonyl-3-phenylpyrazoles and their use as herbicides and for desiccating or defoliating plants
US6075149A (en) * 1995-12-27 2000-06-13 Basf Aktiengesellschaft 2-pyrazolyl oxyphenyl acetic acid derivatives, agents containing them and their use for combating damaging fungi and animal pests
US6319940B1 (en) * 1996-07-24 2001-11-20 Bayer Aktiengesellschaft Carbanilides used as pesticides
US6353116B1 (en) * 1995-08-02 2002-03-05 Smithkline Beecham Corporation Endothelin receptor antagonists
WO2001030154A3 (de) * 1999-10-25 2002-04-11 Basf Ag Pyrazole enthaltende agrochemische zusammensetzungen und ihre verwendung als fungizide flanzenschutzmittel
WO2003041502A1 (en) * 2001-11-13 2003-05-22 Uniroyal Chemical Company Inc. Pesticidal 1-(2-fluorethyl)-4-arylpyrazole derivatives
US20040009353A1 (en) * 1999-06-14 2004-01-15 Knowles Timothy R. PCM/aligned fiber composite thermal interface
US20050080124A1 (en) * 2003-07-22 2005-04-14 Bradley Teegarden Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of disorders related thereto
US20050282868A1 (en) * 2001-08-16 2005-12-22 Finkelstein Bruce L Substituted anthranilamides for controlling invertebrate pests
WO2006045504A1 (en) * 2004-10-21 2006-05-04 Syngenta Participations Ag Process for the preparation of pyrazoles
US20060229335A1 (en) * 2002-12-24 2006-10-12 Bradley Teegarden Diarylamine and arylheteroarylamine pyrazole derivatives as modulators of 5ht2a
US20070207994A1 (en) * 2004-11-19 2007-09-06 Bradley Teegarden 3-Phenyl-pyrazole derivatives as modulators of the 5-HT2a serotonin receptor useful for the treatment of disorders related thereto
US20070293685A1 (en) * 2004-03-23 2007-12-20 Arena Pharmaceuticals, Inc. Processes for Preparing Substituted N-Aryl-N'-[3-(1H-Pyrazol-5-Yl) Phenyl] Ureas and Intermediates Thereof
US20080015223A1 (en) * 2004-12-03 2008-01-17 Arena Pharmaceuticals, Inc. Pyrazole Derivatives as Modulators of the 5-Ht2a Serotonin Receptor Useful for the Treatment of Disorders Related Thereto
US20080200530A1 (en) * 2005-01-19 2008-08-21 Unett David J Diaryl and Arylheteroaryl Urea Derivatives as Modulators of 5-Ht2a Serotonin Receptor Useful for the Prophylaxis or Treatment of Progressive Multifocal Leukoencephalopathy
US20090186895A1 (en) * 2006-05-18 2009-07-23 Arena Pharmaceuticals, Inc. Ethers, secondary amines and derivatives thereof as modulators of the 5-ht2a serotonin receptor useful for the treatment of disorders related thereto
US20090197935A1 (en) * 2006-05-18 2009-08-06 Arena Pharmaceuticals, Inc. Primary amines and derivatives thereof as modulators of the 5-ht2a serotonin receptor useful for the treatment of disorders related thereto
US20100004264A1 (en) * 2006-10-03 2010-01-07 Yifeng Xiong Pyrazole derivatives as modulators of the 5-ht2a serotonin receptor useful for the treatment of disorders related thereto
US20110021538A1 (en) * 2008-04-02 2011-01-27 Arena Pharmaceuticals, Inc. Processes for the preparation of pyrazole derivatives useful as modulators of the 5-ht2a serotonin receptor
US20110207791A1 (en) * 2008-10-28 2011-08-25 Arena Pharmaceuticals, Inc. Composition of a 5-ht2a serotonin receptor modulator useful for the treatment of disorders related thereto
US8481535B2 (en) 2006-05-18 2013-07-09 Arena Pharmaceuticals, Inc. Crystalline forms and processes for the preparation of phenyl-pyrazoles useful as modulators of the 5-HT2A serotonin receptor
US8980891B2 (en) 2009-12-18 2015-03-17 Arena Pharmaceuticals, Inc. Crystalline forms of certain 3-phenyl-pyrazole derivatives as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US9062005B2 (en) 2009-03-03 2015-06-23 E I Du Pont De Nemours And Company Fungicidal pyrazoles
US9126946B2 (en) 2008-10-28 2015-09-08 Arena Pharmaceuticals, Inc. Processes useful for the preparation of 1-[3-(4-bromo-2-methyl-2H-pyrazol-3-yl)-4-methoxy-phenyl]-3-(2,4-difluoro-phenyl)urea and crystalline forms related thereto
US9567327B2 (en) 2007-08-15 2017-02-14 Arena Pharmaceuticals, Inc. Imidazo[1,2-a]pyridine derivatives as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US10022355B2 (en) 2015-06-12 2018-07-17 Axovant Sciences Gmbh Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of REM sleep behavior disorder
US10034859B2 (en) 2015-07-15 2018-07-31 Axovant Sciences Gmbh Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of hallucinations associated with a neurodegenerative disease
EP3868193A4 (en) * 2018-10-18 2022-07-13 Sumitomo Chemical Company, Limited PHENYLPYRAZOLE COMPOUND AND METHOD FOR CONTROLLING PLANT DISEASE

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR9404741A (pt) * 1993-03-25 1999-08-31 Ciba Geigy Ag Herbicidas de triazolpirimidina
FR2705201B1 (fr) * 1993-05-19 1995-07-07 Rhone Poulenc Agrochimie Mélanges herbicides à base de diflufenican et d'un composé 3-phénylpyrazole.
FR2707295A1 (fr) * 1993-06-07 1995-01-13 Rhone Poulenc Agrochimie Fongicides pyrazoles substitués en position 3 par un hétérocycle.
FR2722369B1 (fr) * 1994-07-13 1998-07-10 Rhone Poulenc Agrochimie Compositions fongicides a base de derives 3-phenyl-pyrazoles pour le traitement du materiel vegetal de multiplication, nouveaux derives 3-phenyl-pyrazoles et leurs applications fongicides
AU4632696A (en) * 1995-02-07 1996-08-27 Nissan Chemical Industries Ltd. Pyrazole derivatives and herbicides
JPH09136887A (ja) * 1995-09-13 1997-05-27 Nippon Bayeragrochem Kk クロロピリジルカルボニル誘導体
WO1998043480A1 (fr) * 1997-03-28 1998-10-08 Rhone-Poulenc Agro Compositions fongicides comprenant un 3-phenyl-pyrazole
CZ297590B6 (cs) * 1997-06-23 2007-02-07 Basf Aktiengesellschaft Zpusob prípravy derivátu pyrazolu
FR2773153A1 (fr) * 1997-12-29 1999-07-02 Rhone Poulenc Agrochimie Nouveaux composes fongicides
DE19851986A1 (de) * 1998-11-11 2000-05-18 Bayer Ag Phenyl-substituierte zyklische Enaminone
RU2186772C2 (ru) * 1999-11-11 2002-08-10 Иркутский институт химии СО РАН Производные 1-метил-5-хлорпиразола и способ их получения
DE10063865A1 (de) * 2000-12-21 2002-06-27 Bayer Ag Verwendung von Pyrazoloximen als Parasitizide
NZ529403A (en) 2001-04-10 2005-06-24 Pfizer Pyrazole derivatives for treating HIV
AU2003275093A1 (en) * 2002-09-24 2004-04-19 Arena Pharmaceuticals, Inc. Process of making phenylpyrazoles useful as selective 5ht2a modulators and intermediates thereof
US20040157738A1 (en) * 2003-02-12 2004-08-12 Ishihara Sangyo Kaisha, Ltd. Novel oxygen containing fused cyclic derivatives and herbicidal, desiccant and defoliate compositions containing them
ES2398854T3 (es) 2007-04-03 2013-03-22 E. I. Du Pont De Nemours And Company Fungicidas de benceno sustituido
EP2628722A1 (en) * 2012-02-16 2013-08-21 Bayer CropScience AG CF3O-containing enaminoketones and their utilization for the preparation of CF3O-containing pyrazoles
WO2015157005A1 (en) 2014-04-10 2015-10-15 E I Du Pont De Nemours And Company Substituted tolyl fungicide mixtures
AR121893A1 (es) * 2020-04-22 2022-07-20 Sumitomo Chemical Co Compuesto de fenilo y método para controlar enfermedades vegetales
JPWO2022250069A1 (cs) * 2021-05-26 2022-12-01
AR130609A1 (es) 2022-09-30 2024-12-18 Sumitomo Chemical Co Compuesto de fenilpirazol y método para controlar enfermedades vegetales

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2721143A (en) * 1950-11-18 1955-10-18 Knoll Ag 3-phenyl pyrazol compounds and preserved composition containing said compounds

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ178996A (en) 1974-11-15 1978-06-02 Kornis G Pyrfazole amides and thioamides;herbicidal compositions
US4245106A (en) 1979-07-05 1981-01-13 Monsanto Company Process for the preparation of 1-alkyl-3-aryl-4-pyrazolecarboxylates
DE3331692A1 (de) * 1983-09-02 1985-03-28 Basf Ag, 6700 Ludwigshafen 3-phenyl-4-methoxycarbonylpyrazole, verfahren zu ihrer herstellung und ihre verwendung zur bekaempfung unerwuenschten pflanzenwuchses
US4843068A (en) * 1985-12-27 1989-06-27 Nihon Nohyaku Co., Ltd. Pyrazole oxime derivatives and compositions
US4792565A (en) * 1986-04-24 1988-12-20 Mitsui Toatsu Chemicals, Inc. Pyrazolecarbonylamine derivatives and agricultural and horticultural fungicides containing said compounds
AU616564B2 (en) * 1988-09-29 1991-10-31 Sumitomo Chemical Company, Limited Novel pyrazole compounds, method for production thereof, use thereof and intermediates for production thereof
PH27357A (en) * 1989-09-22 1993-06-21 Fujisawa Pharmaceutical Co Pyrazole derivatives and pharmaceutical compositions comprising the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2721143A (en) * 1950-11-18 1955-10-18 Knoll Ag 3-phenyl pyrazol compounds and preserved composition containing said compounds

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts Online 111:194660; 1988. *
Nawrot Modranka et al, Polish Journal of Chemistry , 62, 417 426 (1988). *
Nawrot-Modranka et al, Polish Journal of Chemistry, 62, 417-426 (1988).

Cited By (83)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5945382A (en) * 1992-04-27 1999-08-31 Rhone-Poulenc Agrochimie Fungicidal arylpyrazoles
US5962489A (en) * 1992-07-16 1999-10-05 Basf Aktiengesellschaft Heteroaromatic compounds and crop protection agents containing them
US5817682A (en) * 1992-07-16 1998-10-06 Basf Aktiengesellschaft Heteroaromatic compounds and crop protection agents containing them
US5856514A (en) * 1993-06-03 1999-01-05 Rhone-Poulenc Agrochimie Arylpyrazole fungicides
US6353116B1 (en) * 1995-08-02 2002-03-05 Smithkline Beecham Corporation Endothelin receptor antagonists
US6482956B2 (en) * 1995-08-02 2002-11-19 Smithkline Beecham Corporation Endothelin receptor antagonists
US6075149A (en) * 1995-12-27 2000-06-13 Basf Aktiengesellschaft 2-pyrazolyl oxyphenyl acetic acid derivatives, agents containing them and their use for combating damaging fungi and animal pests
US6319940B1 (en) * 1996-07-24 2001-11-20 Bayer Aktiengesellschaft Carbanilides used as pesticides
US6054413A (en) * 1996-09-19 2000-04-25 Basf Aktiengesellschaft 1-sulfonyl-3-phenylpyrazoles and their use as herbicides and for desiccating or defoliating plants
WO2000013508A1 (en) * 1998-09-09 2000-03-16 Ishihara Sangyo Kaisha, Ltd. Fused-benzene derivatives useful as herbicides
US6573218B1 (en) 1998-09-09 2003-06-03 Ishihara Sangyo Kaisha, Ltd. Fused-benzene derivatives useful as herbicides
US20040009353A1 (en) * 1999-06-14 2004-01-15 Knowles Timothy R. PCM/aligned fiber composite thermal interface
WO2001030154A3 (de) * 1999-10-25 2002-04-11 Basf Ag Pyrazole enthaltende agrochemische zusammensetzungen und ihre verwendung als fungizide flanzenschutzmittel
US20070203201A1 (en) * 2001-08-16 2007-08-30 Finkelstein Bruce L Substituted anthranilamides for controlling invertebrate pests
US7199138B2 (en) 2001-08-16 2007-04-03 E. I. Du Pont De Nemours And Company Substituted anthranilamides for controlling invertebrate pests
US20050282868A1 (en) * 2001-08-16 2005-12-22 Finkelstein Bruce L Substituted anthranilamides for controlling invertebrate pests
US7541377B2 (en) 2001-08-16 2009-06-02 E.I. Du Pont De Nemours And Company Substituted anthranilamides for controlling invertebrate pests
WO2003041502A1 (en) * 2001-11-13 2003-05-22 Uniroyal Chemical Company Inc. Pesticidal 1-(2-fluorethyl)-4-arylpyrazole derivatives
US20060229335A1 (en) * 2002-12-24 2006-10-12 Bradley Teegarden Diarylamine and arylheteroarylamine pyrazole derivatives as modulators of 5ht2a
US20070072857A1 (en) * 2003-07-22 2007-03-29 Arena Pharmaceuticals Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of disorders related thereto
US8754238B2 (en) 2003-07-22 2014-06-17 Arena Pharmaceuticals, Inc. Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of disorders related thereto
US8871797B2 (en) 2003-07-22 2014-10-28 Arena Pharmaceuticals, Inc. Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of disorders related thereto
US20050080124A1 (en) * 2003-07-22 2005-04-14 Bradley Teegarden Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of disorders related thereto
US9273035B2 (en) 2003-07-22 2016-03-01 Arena Pharmaceuticals, Inc. Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of disorders related thereto
US9775829B2 (en) 2003-07-22 2017-10-03 Arena Pharmaceuticals, Inc. Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of disorders related thereto
US7812176B2 (en) 2004-03-23 2010-10-12 Arena Pharmaceuticals, Inc. Processes for preparing substituted N-aryl-N′-[3-(1H-pyrazol-5-YL) phenyl] ureas and intermediates thereof
US20070293685A1 (en) * 2004-03-23 2007-12-20 Arena Pharmaceuticals, Inc. Processes for Preparing Substituted N-Aryl-N'-[3-(1H-Pyrazol-5-Yl) Phenyl] Ureas and Intermediates Thereof
US7678924B2 (en) 2004-10-21 2010-03-16 Syngenta Crop Protection, Inc. Process for the preparation of pyrazoles
EA010851B1 (ru) * 2004-10-21 2008-12-30 Зингента Партисипейшнс Аг Способ получения пиразолов
JP2008517019A (ja) * 2004-10-21 2008-05-22 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト ピラゾールの調製のための方法
AU2005298922B2 (en) * 2004-10-21 2012-01-19 Syngenta Participations Ag Process for the preparation of pyrazoles
WO2006045504A1 (en) * 2004-10-21 2006-05-04 Syngenta Participations Ag Process for the preparation of pyrazoles
US10781180B2 (en) 2004-11-19 2020-09-22 Arena Pharmaceuticals, Inc. 3-phenyl-pyrazole derivatives as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US20070244086A1 (en) * 2004-11-19 2007-10-18 Arena Pharmaceuticals, Inc. 3-Phenyl-Pyrazole Derivatives as Modulators of the 5-Ht2A Serotonin Receptor Useful for the Treatment of Disorders Related Thereto
US20070207994A1 (en) * 2004-11-19 2007-09-06 Bradley Teegarden 3-Phenyl-pyrazole derivatives as modulators of the 5-HT2a serotonin receptor useful for the treatment of disorders related thereto
US7884101B2 (en) 2004-11-19 2011-02-08 Arena Pharmaceuticals, Inc. 3-phenyl-pyrazole derivatives as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US20110105456A1 (en) * 2004-11-19 2011-05-05 Bradley Teegarden 3-phenyl-pyrazole derivatives as modulators of the 5-ht2a serotonin receptor useful for the treatment of disorders related thereto
US8785441B2 (en) 2004-11-19 2014-07-22 Arena Pharmaceuticals, Inc. 3-phenyl-pyrazole derivatives as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US20080015223A1 (en) * 2004-12-03 2008-01-17 Arena Pharmaceuticals, Inc. Pyrazole Derivatives as Modulators of the 5-Ht2a Serotonin Receptor Useful for the Treatment of Disorders Related Thereto
US20080200530A1 (en) * 2005-01-19 2008-08-21 Unett David J Diaryl and Arylheteroaryl Urea Derivatives as Modulators of 5-Ht2a Serotonin Receptor Useful for the Prophylaxis or Treatment of Progressive Multifocal Leukoencephalopathy
US8148418B2 (en) 2006-05-18 2012-04-03 Arena Pharmaceuticals, Inc. Ethers, secondary amines and derivatives thereof as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US9328107B2 (en) 2006-05-18 2016-05-03 Arena Pharmaceuticals, Inc. Primary amines and derivatives thereof as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US8664258B2 (en) 2006-05-18 2014-03-04 Arena Pharmaceuticals, Inc. Primary amines and derivatives thereof as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US8680119B2 (en) 2006-05-18 2014-03-25 Arena Pharmaceuticals, Inc. Ethers, secondary amines and derivatives thereof as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US8148417B2 (en) 2006-05-18 2012-04-03 Arena Pharmaceuticals, Inc. Primary amines and derivatives thereof as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US20090197935A1 (en) * 2006-05-18 2009-08-06 Arena Pharmaceuticals, Inc. Primary amines and derivatives thereof as modulators of the 5-ht2a serotonin receptor useful for the treatment of disorders related thereto
US20090186895A1 (en) * 2006-05-18 2009-07-23 Arena Pharmaceuticals, Inc. Ethers, secondary amines and derivatives thereof as modulators of the 5-ht2a serotonin receptor useful for the treatment of disorders related thereto
USRE45337E1 (en) 2006-05-18 2015-01-13 Arena Pharmaceuticals, Inc. Ethers, secondary amines and derivatives thereof as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
USRE45336E1 (en) 2006-05-18 2015-01-13 Arena Pharmaceuticals, Inc. Primary amines and derivatives thereof as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US10450276B2 (en) 2006-05-18 2019-10-22 Arena Pharmaceuticals, Inc. Ethers, secondary amines and derivatives thereof as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US9987252B2 (en) 2006-05-18 2018-06-05 Arena Pharmaceuticals, Inc. Primary amines and derivitves thereof as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US8481535B2 (en) 2006-05-18 2013-07-09 Arena Pharmaceuticals, Inc. Crystalline forms and processes for the preparation of phenyl-pyrazoles useful as modulators of the 5-HT2A serotonin receptor
US9783502B2 (en) 2006-05-18 2017-10-10 Arena Pharmaceuticals, Inc. Crystalline forms and processes for the preparation of phenyl-pyrazoles useful as modulators of the 5-HT2A serotonin receptor
US9199940B2 (en) 2006-05-18 2015-12-01 Arena Pharmaceuticals, Inc. Crystalline forms and processes for the preparation of phenyl-pyrazoles useful as modulators of the 5-HT2A serotonin receptor
US9221755B2 (en) 2006-05-18 2015-12-29 Arena Pharmaceuticals, Inc. Ethers, secondary amines and derivatives thereof as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US20100004264A1 (en) * 2006-10-03 2010-01-07 Yifeng Xiong Pyrazole derivatives as modulators of the 5-ht2a serotonin receptor useful for the treatment of disorders related thereto
US10351531B2 (en) 2006-10-03 2019-07-16 Arena Pharmaceuticals, Inc. Pyrazole derivatives as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US9434692B2 (en) 2006-10-03 2016-09-06 Arena Pharmaceuticals, Inc. Pyrazole derivatives as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US9732039B2 (en) 2006-10-03 2017-08-15 Arena Pharmeceuticals, Inc. Pyrazole derivatives as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US10058549B2 (en) 2007-08-15 2018-08-28 Arena Pharmaceuticals, Inc. Imidazo[1,2-α]pyridine derivatives as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US9567327B2 (en) 2007-08-15 2017-02-14 Arena Pharmaceuticals, Inc. Imidazo[1,2-a]pyridine derivatives as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US10787437B2 (en) 2008-04-02 2020-09-29 Arena Pharmaceuticals, Inc. Processes for the preparation of pyrazole derivatives useful as modulators of the 5-HT2A serotonin receptor
US9556149B2 (en) 2008-04-02 2017-01-31 Arena Pharmaceuticals, Inc. Processes for the preparation of pyrazole derivatives useful as modulators of the 5-HT2A serotonin receptor
US20110021538A1 (en) * 2008-04-02 2011-01-27 Arena Pharmaceuticals, Inc. Processes for the preparation of pyrazole derivatives useful as modulators of the 5-ht2a serotonin receptor
US9745270B2 (en) 2008-10-28 2017-08-29 Arena Pharmaceuticals, Inc. Processes useful for the preparation of 1-[3-(4-bromo-2-methyl-2H-pyrazol-3-yl)-4-methoxy-phenyl]-3-(2,4-difluoro-phenyl)-urea and crystalline forms related thereto
US9353064B2 (en) 2008-10-28 2016-05-31 Arena Pharmaceuticals, Inc. Processes useful for the preparation of 1-[3-(4-bromo-2-methyl-2H-pyrazol-3-yl)-4-methoxy-phenyl]-3-(2,4-difluoro-phenyl)-urea and crystalline forms related thereto
US9126946B2 (en) 2008-10-28 2015-09-08 Arena Pharmaceuticals, Inc. Processes useful for the preparation of 1-[3-(4-bromo-2-methyl-2H-pyrazol-3-yl)-4-methoxy-phenyl]-3-(2,4-difluoro-phenyl)urea and crystalline forms related thereto
US9801856B2 (en) 2008-10-28 2017-10-31 Arena Pharmaceuticals, Inc. Composition of a 5-HT2A serotonin receptor modulator useful for the treatment of disorders related thereto
US9034911B2 (en) 2008-10-28 2015-05-19 Arena Pharmaceuticals, Inc. Composition of a 5-HT2A serotonin receptor modulator useful for the treatment of disorders related thereto
US10583122B2 (en) 2008-10-28 2020-03-10 Arena Pharmaceuticals, Inc. Composition of a 5-HT2A serotonin receptor modulator useful for the treatment of disorders related thereto
US10543193B2 (en) 2008-10-28 2020-01-28 Arena Pharmaceuticals, Inc. Processes useful for the preparation of 1-[3-(4-bromo-2-methyl-2H-pyrazol-3-yl)-4-methoxy-phenyl]-3-(2,4-difluoro-phenyl)-urea and crystalline forms related thereto
US10071075B2 (en) 2008-10-28 2018-09-11 Arena Pharmaceuticals, Inc. Processes useful for the preparation of 1-[3-(4-bromo-2-methyl-2H-pyrazol-3-yl)-4-methoxy-phenyl]-3-(2,4-difluoro-phenyl)-urea and crystalline forms related thereto
US10117851B2 (en) 2008-10-28 2018-11-06 Arena Pharmaceuticals, Inc. Composition of a 5-HT2A serotonin receptor modulator useful for the treatment of disorders related thereto
US20110207791A1 (en) * 2008-10-28 2011-08-25 Arena Pharmaceuticals, Inc. Composition of a 5-ht2a serotonin receptor modulator useful for the treatment of disorders related thereto
US9062005B2 (en) 2009-03-03 2015-06-23 E I Du Pont De Nemours And Company Fungicidal pyrazoles
US10448639B2 (en) 2009-03-03 2019-10-22 Fmc Corporation Fungicidal pyrazoles
US9655361B2 (en) 2009-03-03 2017-05-23 E I Du Pont De Nemours And Company Fungicidal pyrazoles
US8980891B2 (en) 2009-12-18 2015-03-17 Arena Pharmaceuticals, Inc. Crystalline forms of certain 3-phenyl-pyrazole derivatives as modulators of the 5-HT2A serotonin receptor useful for the treatment of disorders related thereto
US10022355B2 (en) 2015-06-12 2018-07-17 Axovant Sciences Gmbh Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of REM sleep behavior disorder
US10034859B2 (en) 2015-07-15 2018-07-31 Axovant Sciences Gmbh Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of hallucinations associated with a neurodegenerative disease
US11304932B2 (en) 2015-07-15 2022-04-19 Axovant Sciences Gmbh Diaryl and arylheteroaryl urea derivatives as modulators of the 5-HT2A serotonin receptor useful for the prophylaxis and treatment of hallucinations associated with a neurodegenerative disease
EP3868193A4 (en) * 2018-10-18 2022-07-13 Sumitomo Chemical Company, Limited PHENYLPYRAZOLE COMPOUND AND METHOD FOR CONTROLLING PLANT DISEASE
US12225904B2 (en) 2018-10-18 2025-02-18 Sumitomo Chemical Company, Limited Phenylpyrazole compound and method for controlling plant disease

Also Published As

Publication number Publication date
AP377A (en) 1995-02-17
HRP921023A2 (en) 1996-04-30
KR100255682B1 (ko) 2000-05-01
YU48425B (sh) 1998-07-10
YU91392A (sh) 1995-03-27
MA22675A1 (fr) 1993-07-01
ZW16192A1 (en) 1993-06-02
FR2682379B1 (fr) 1994-02-11
HU215380B (hu) 1999-04-28
JPH061769A (ja) 1994-01-11
CA2080195A1 (en) 1993-04-10
ZA927718B (en) 1993-11-15
BG96961A (bg) 1993-12-24
RU2072991C1 (ru) 1997-02-10
PL296208A1 (en) 1993-12-13
RO110944B1 (ro) 1996-05-30
BR9204011A (pt) 1993-04-27
BG62255B1 (bg) 1999-06-30
PL172376B1 (pl) 1997-09-30
MY113369A (en) 2002-02-28
AU2630192A (en) 1993-04-22
CN1131151A (zh) 1996-09-18
PH30759A (en) 1997-10-17
AP9200433A0 (en) 1992-10-31
FI924557A0 (fi) 1992-10-08
SK279059B6 (sk) 1998-06-03
KR930007908A (ko) 1993-05-20
FI111541B (fi) 2003-08-15
FR2682379A1 (fr) 1993-04-16
CZ283473B6 (cs) 1998-04-15
AU665782B2 (en) 1996-01-18
US5663119A (en) 1997-09-02
CZ306592A3 (en) 1993-08-11
CN1071162A (zh) 1993-04-21
IL103408A0 (en) 1993-03-15
PL299872A1 (en) 1994-04-05
HUT64033A (en) 1993-11-29
NZ244671A (en) 1995-05-26
JP3504679B2 (ja) 2004-03-08
SI9200254A (en) 1993-06-30
CN1050834C (zh) 2000-03-29
MX9205768A (es) 1993-04-01
HU9203184D0 (en) 1992-12-28
FI924557L (fi) 1993-04-10
ECSP920870A (es) 1993-11-01
EG19893A (fr) 1996-03-31
EP0538156A1 (fr) 1993-04-21
SK306592A3 (en) 1995-10-11
IL103408A (en) 1997-02-18

Similar Documents

Publication Publication Date Title
US5523280A (en) Phenylpyrazole fungicides
US5945382A (en) Fungicidal arylpyrazoles
FI119732B (fi) Fungisidiset 2-imidatsolin-5-oni- ja 2-imidatsoliini-5-tionijohdannaiset ja menetelmä niiden valmistamiseksi
CZ9197A3 (en) Fungicidal agents containing derivatives of 3-phenylpyrazole, novel derivatives of 3-phenylpyrazole and their use as fungicides
SK278689B6 (sk) Semikarbazóny a tiosemikarbazóny
US4783459A (en) Anilinopyrimidine fungicides
SK161494A3 (en) 2-imidazoline-5-one and 2-imidazoline-5-thione derivatives, method of their preparation and fungicidal composition containing these derivatives
EP0432892A1 (en) Imidazole fungicides
KR20070003935A (ko) 피리미딘 유도체 및 농원예용 살진균제로서의 그의 용도
AU679731B2 (en) Nicotinic acid derivative and herbicide
JP2007518675A (ja) 抗真菌性フェノキシフェニルヒドラジン誘導体
HU222255B1 (hu) Fungicid hatású 2-imidazolin-5-on és 2-imidazolin-5-tion-származékok

Legal Events

Date Code Title Description
AS Assignment

Owner name: RHONE-POULENC AGROCHIMIE, FRANCE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:CHENE, ALAIN;PEIGNIER, RAYMOND;VORS, JEAN-PIERRE A.;AND OTHERS;REEL/FRAME:006330/0553;SIGNING DATES FROM 19921102 TO 19921109

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20080604